JP2723348B2 - Epoxy resin composition for semiconductor encapsulation - Google Patents

Description

The present invention relates to an epoxy resin composition for semiconductor encapsulation.
More specifically, a modified silicone oil having a hydroxyphenyl group and a modified silicone oil having an epoxy group or a modified silicone oil having a hydroxyphenyl group and a modified silicone oil having an epoxy group and a bifunctional epoxy resin are used as a flexibilizing agent. Epoxy resin composition for semiconductor encapsulation using a novel copolymer, retaining the original moisture resistance and heat resistance of epoxy resin,
The present invention also relates to an epoxy resin composition for semiconductor encapsulation that provides a cured product having a low elastic modulus, a low expansion coefficient, a high glass transition temperature, and a high toughness.

[Problems to be Solved by Conventional Techniques] In recent years, semiconductor elements have become larger in chip area with higher integration, and thinner in resin, and have been sealed with a conventional epoxy resin composition. When a semiconductor component is manufactured by such a method, there is a problem that cracks are likely to be generated in the chip, cutting of bonding wires, sliding of aluminum wiring, cracking of sealing resin, and the like. These are fatal failures for semiconductor components. This is because a conventional epoxy resin composition for semiconductor encapsulation has been developed mainly from the viewpoint of improving heat resistance and moisture resistance, and the cured product has poor flexibility and large stress applied to the element. It is.

In general, methods for reducing the stress of an epoxy resin composition for semiconductor encapsulation include a method of reducing the thermal expansion by reducing the coefficient of thermal expansion of the resin, and a method of reducing the stress due to the thermal distortion by reducing the elastic modulus. It has been known. Further, in order to widen the temperature range where the thermal strain is small while maintaining heat resistance and moisture resistance, it is necessary to increase the glass transition temperature.

As a method of reducing the stress, there is a method of adding a flexibilizing agent. However, a conventionally used flexibilizing agent (for example, having a long-chain alkylene polyamine, a polyoxyalkylene glycol, or a long-chain alkylene oxide The method of lowering the elastic modulus by incorporating bisphenol A-type diglycidyl ether) has the disadvantage that the glass transition temperature of the cured product is greatly reduced, and the heat resistance and moisture resistance are reduced (Japanese Patent Publication No. 59-8718). Gazette, JP-A-59-30820, JP-A-59-226066, etc.).

On the other hand, as a flexible agent having a small decrease in moisture resistance and glass transition temperature, there are polybutadiene having a functional group capable of reacting with an epoxy resin at both terminals, and an elastomer-modifiable polymer obtained from a copolymer of butadiene and acrylonitrile. Flexing agents have also been considered (JP-A-58-174416,
JP-B-58-108220, JP-A-58-184204, JP-B-62-9248, JP-A-59-113021, JP-A-58-11302
No. 59-58024). However, the elastomer-modified flexible agent has a problem in that the unsaturated bond in the elastomer is oxidized and deteriorated at a high temperature, so that the effect of the flexibility is lost.

There is also known a method of dispersing a low elastic modulus silicone resin or silicone rubber, which is a flexible agent excellent in electrical properties and thermal stability at high temperatures (Japanese Patent Application Laid-Open No. Sho 62-62).
No. 84147, JP-A-56-4647, JP-A-64-29450
No., etc.). However, silicone resin has poor adhesion to metal, and silicone rubber has low interfacial strength with epoxy matrix, so the cured product has high moisture permeability,
There is a problem that reliability is impaired in that moisture resistance is poor and mechanical strength is weak.

The present inventors have found that an epoxy resin composition using a pre-reaction product of a modified silicone oil having an epoxy group and a phenol novolak resin as a flexible agent has heat resistance and moisture resistance, and has a low elastic modulus. (See JP-B-62-83158, which has already been found to provide a cured product).
It has already been shown that the pre-reacted product of a modified silicone oil having a hydroxyphenyl group and an epoxy resin gives a cured product having heat resistance, moisture resistance, a low elastic modulus, a low coefficient of thermal expansion, and a high glass transition temperature. Heading (Japanese Patent Application No. 63
-115269 and Japanese Patent Application No. 63-161849).

[Means for Solving the Problems] In addition to the properties of the resin composition, namely, heat resistance, moisture resistance, low elastic modulus, low coefficient of thermal expansion, and high glass transition temperature, the present invention further provides fine dispersion of silicone. Accordingly, an object of the present invention is to obtain an epoxy resin composition for semiconductor encapsulation that gives a cured product having higher toughness than conventional ones.

That is, the present invention provides a compound represented by the general formula (I): (Wherein, R ^{1 to} R ³ are each a divalent organic group, R ^{4 to} R ¹⁰ are each an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxyalkyl having 1 to 10 carbon atoms. A group, a phenyl group or a fluorine-substituted alkyl group having 1 to 10 carbon atoms, a
Is an integer of 5-300, b is an integer of 0-10, provided that 0 ≦ [b /
(A + b)] ≦ 0.32) a modified silicone oil having a hydroxyphenyl group, and a general formula (II): (Wherein, R ^{11 to} R ¹³ are each a divalent organic group, R ^{14 to} R ²⁰ are each an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxyalkyl having 1 to 10 carbon atoms. Group, a phenyl group or a fluorine-substituted alkyl group having 1 to 10 carbon atoms,
c is an integer of 5-300, d is an integer of 0-10, provided that 0 ≦ [d
/(C+d)]≦0.32) or a copolymer with a modified silicone oil having an epoxy group or the general formula (I)
And a modified silicone oil having an epoxy group represented by the general formula (II) and a modified silicone oil having an epoxy group represented by the general formula (III): (Wherein, R ²¹ and R ²² are each a direct bond or a divalent organic group, e is an integer of 0 to 20, and a hydrogen atom of a benzene ring may be substituted). Contains a terminal and / or internal hydroxyphenyl group-containing silicone composed of a copolymer with an epoxy resin having a group as a flexibilizer, epoxy resin, curing agent, curing accelerator, filler, release agent, coloring The present invention relates to an epoxy resin composition for semiconductor encapsulation, comprising an agent and a surface treatment agent.

[Function] The flexibilizer used in the present invention comprises a phenolic hydroxyl group contained in a modified silicone oil, an epoxy group contained in another modified silicone oil or a phenolic hydroxyl group contained in a modified silicone oil, and another modified A block or graft copolymer in which an epoxy group contained in silicone oil and an epoxy group contained in a bifunctional epoxy resin react with each other to have a hydrocarbon portion between polymer chains of silicone. The compatibility between the silicone and the epoxy resin as the main component can be increased, and the toughness can be increased. Further, since the flexibilizer contains a hydroxyphenyl group, it can react with the epoxy resin, and the exudation and mold release during molding are improved.

Examples Specific examples of the epoxy resin used as a main component of the composition of the present invention include, for example, a cresol novolak epoxy resin, a phenol novolak epoxy resin, an alkylbenzene-modified phenol novolak epoxy resin, and a halogenated phenol novolak epoxy resin. ,
Examples include bisphenol A novolak type epoxy resins and multifunctional epoxy resins such as tris (glycidoxyphenyl) methane. In addition, not only a novolak epoxy resin and a polyfunctional epoxy resin but also a bifunctional epoxy resin may be used. Specific examples of the bifunctional epoxy resin include bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol Examples include F-type epoxy resins, bisphenol-type epoxy resins, heterocyclic skeleton epoxy resins such as naphthalene, and all types of epibis-type epoxy resins having epoxy groups at both ends. Further, there may be mentioned, for example, epoxy resins having a structure in which the epoxy resin has various substituents, but is not limited thereto.

These epoxy resins may be used alone or in combination of two or more.

Specific examples of the curing agent used in the present invention include, for example, phenol curing agents such as phenol novolak resins, cresol novolak resins, alkyl-modified phenol resins, bisphenol A novolak resins, and polyfunctional phenol resins such as tris (hydroxyphenyl) methane. And acid anhydrides and polyfunctional amino compounds.
It is not limited to these. These may be used alone or in combination of two or more.

The terminal and / or internal hydroxyphenyl group-containing silicone (hereinafter, referred to as “flexible agent”) used in the present invention
The compound represented by the general formula (I): A modified silicone oil having a hydroxyphenyl group represented by (hereinafter also referred to as a modified silicone oil A)
And the general formula (II): A modified silicone oil having an epoxy group represented by the following formula (hereinafter also referred to as modified silicone oil B) or modified silicone oil A, modified silicone oil B and general formula (III): And a copolymer with an epoxy resin having epoxy groups at both ends represented by (hereinafter, also referred to as a bifunctional epoxy resin). The arrangement of the repeating units in the general formula (I) or (II) is not limited, and may be random copolymerization or block copolymerization.

Therefore, the flexibilizer used in the present invention may be a copolymer of modified silicone oil A and modified silicone oil B, or a copolymer of modified silicone oil A, modified silicone oil B and a bifunctional epoxy resin. It may be a polymer or a combination of these copolymers.

When the modified silicone oil B is used, a highly compatible organic bonding portion can be provided between the modified silicone oil A and the modified silicone oil B, and a highly compatible silicone oil is produced. When a bifunctional epoxy resin is used, a structure in which a highly compatible bifunctional epoxy resin is bonded between two modified silicone oils A, for example, can be provided with toughness.

The modified silicone oil A or the modified silicone oil B is a component that functions as a compatibilizer when the average molecular weight is 2,000 or less, and as a low elastic modulus agent when the silicone oil has an average molecular weight of more than 2,000.

R ^{1 to} R ³ in the general formula (I) are each a divalent organic group, and specific examples thereof include, for example, a methylene group,
1 carbon atom such as ethylene group, propylene group, butylene group
5 alkylene _{group, -C 3 H 6 OC 3 H} 6 - ethers such structure, a heterocyclic structure, bicyclo skeleton, biphenyl skeleton. The b R ² may be the same or different.

R ^{4 to} R ¹⁰ each have a carbon number of 1 to 10, preferably a carbon number such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, a pentyl group and an isopentyl group. Alkyl groups having 1 to 5 carbon atoms, such as methoxy, ethoxy, propoxy and the like, preferably alkoxy groups having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, such as HOCH _2- , (HO) ₂ CH-, HO-CH ₂ −CH
_{2 -, HO-C 3 H} 6 -, (HOCH 2) 2 CH- carbon atoms such as 1 to 10, preferably a hydroxyalkyl group having 1 to 5 carbon atoms, a phenyl group, or, for example, CF ₃ CH ₂ CH ₂ - , CF ₃ (CF ₂ ) ₂ CH ₂ CH ₂
And a fluorine-substituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. In addition, a number of R ⁶ , a number of R ⁷ ,
b number of R ⁸ may be each the same kind, it may be heterologous.

a is an integer of 5-300, preferably 7-250. When a is less than 5, there is no effect as a flexibilizing agent, and heat resistance is reduced. When it exceeds 300, strength is extremely reduced.

Further, b / (a + b) is 0 to 0.32, preferably 0 to 0.
25. If b / (a + b) exceeds 0.32, the number of rejuvenating groups is too large, so that gelation occurs or the effect as an elastomer decreases.

The hydroxyl equivalent of the hydroxyphenyl group of the modified silicone oil A is preferably from 100 to 13000, and more preferably from 250 to 8000. The number of hydroxyphenyl groups per molecule is preferably from 2 to 12. When the hydrogen group equivalent of the hydroxyphenyl group or the number of hydroxyphenyl groups per molecule is out of the above range, when the number of hydroxyphenyl groups is small, the reaction at the time of reaction with the modified silicone oil B or the bifunctional epoxy resin is sufficient. Tend to stop progressing,
In addition, when there are many hydroxyphenyl groups, there is a tendency to gel during the reaction.

Preferred examples of the modified silicone oil A include, for example, And so on.

In the above general formula (II) showing the modified silicone oil B,
R ^{11 to} R ¹³ are the same divalent organic machines as R ^{1 to} R ³ , respectively. d number of R ¹² may be the same type, it may be heterologous.

R ^{14 to} R ²⁰ are the same alkyl group, alkoxy group, hydroxyalkyl group, phenyl group or fluorine-substituted alkyl group as R ^{4 to} R ^10, respectively. c R ¹⁶ , c R ¹⁷ , and d R ¹⁸ may be the same or different.

c is an integer of 5-300, preferably 7-250. c5
If the amount is less than the above, there is no effect as a flexibilizing agent, and the heat resistance is reduced. If the amount exceeds 300, the strength is extremely reduced.

Further, d / (c + d) is 0 to 0.32, preferably 0 to 0.
25. If d / (c + d) exceeds 0.32, the number of functional groups is too large, so that gelation occurs or the effect as an elastomer is reduced.

The epoxy equivalent of the epoxy group of the modified silicone oil B is preferably from 100 to 13000, more preferably from 250 to 8000. The number of epoxy groups per molecule is preferably 2 to 12. If the epoxy equivalent or the number of epoxy groups per molecule is out of the above range, the reaction tends not to proceed sufficiently during the reaction with the silicone oil A if the epoxy group is small, and if the epoxy group is large, In time,
It tends to gel during the reaction.

Preferred examples of the modified silicone oil B include, for example, And so on.

R in the above general formula (III) representing a bifunctional epoxy resin
²¹ and R ²² are each a direct bond or a divalent organic machine similar to the aforementioned R ^{1 to} R ³ . may be the e number of R ²² the same kind, it may be heterologous.

e is an integer of 0-20, preferably 0-16. e w2
If it exceeds 0, the chain becomes too long and the heat resistance decreases.

The hydrogen atom of the benzene ring in the general formula (III) may be substituted with, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a t-butyl group, or a fluorine group.

Preferred examples of the bifunctional epoxy resin include, for example, And so on.

The flexibilizer used in the present invention comprises one or more modified silicone oils A and one or more modified silicone oils B or one or more modified silicone oils A and one or more modified silicone oils B and a difunctional agent. Epoxy resin 1
More than one kind is defined as the hydroxyl group (also referred to as phenolic hydroxyl group) of the hydroxyphenyl group of the modified silicone oil A and the epoxy group of the modified silicone oil B or the phenolic hydroxyl group of the modified silicone oil A and the modified silicone oil and the bifunctional epoxy resin. It is preferable that the reaction is carried out at a ratio such that the equivalent ratio with the epoxy group (phenolic hydroxyl group / epoxy group) is 1 to 30, especially silicone oil A having a hydroxyphenyl group inside the molecule.
When is used, the ratio is preferably 5 to 30 from the viewpoint of preventing gelation.

Further, it is preferable that 70% or more, more preferably 90% or more, of the epoxy groups of the modified silicone oil B and the bifunctional epoxy resin have reacted with the phenolic hydroxyl groups of the modified silicone oil A. When the number of unreacted epoxy groups increases, it becomes difficult to react with the epoxy resin.

Reaction of modified silicone oil A with modified silicone oil B or modified silicone oil A with modified silicone oil B and bifunctional epoxy resin (preliminary reaction)
Is usually carried out in a nitrogen atmosphere using an amine compound, an imidazole compound, a phosphorus compound or the like as a catalyst.

Specific examples of the amine compound used as the catalyst include trimethylamine and tetramethylammonium hydroxide. Specific examples of the imidazole compound include 2-ethyl-4-methylimidazole and 2-methylimidazole. Specific examples include triphenylphosphine, tri-t-butylphosphine, and organic salts thereof.

The proportion of the flexibilizer in the composition of the present invention is expressed by the following formula: X is the total weight of the modified silicone oil A and the modified silicone oil B when the modified silicone oil A is used, and Assuming that the weight of an organic component such as an epoxy resin and a curing agent (including a bifunctional epoxy resin for a flexible agent when the bifunctional epoxy resin is used) is Y, X / (X + Y) is 0.03 to The ratio is preferably 0.4, more preferably 0.05 to 0.2. If this value is less than 0.03, not only the effect of lowering the elastic modulus of the obtained molded article and the improvement of the glass transition temperature are small, but also the decrease in the coefficient of thermal expansion tends to be small. Conversely 0.4
Exceeding this will lower the mechanical strength.

In the composition of the present invention, the reaction between the total of the equivalents of the epoxy groups of the epoxy resin used as the main component and the epoxy groups in the flexibilizer and the epoxy groups such as phenolic hydroxyl groups in the curing agent and the flexibilizer. It is preferred for the purposes of the present invention that the ratio of the groups involved in the reaction to the sum of the equivalents (epoxy groups / groups involved in the reaction with the epoxy groups) is in the range from 0.7 to 1.3.

The curing accelerator used in the present invention is not particularly limited as long as it is a usual catalyst. Specific examples thereof include a phosphorus compound represented by a phosphine such as triphenylphosphine, Imidazoles such as imidazole and 2-ethyl-4-methylimidazole; tertiary amines; 1,8-diazabicyclo (5,4,0) undecene-7; and organic salts thereof. These may be used alone or in combination of two or more.

The addition amount of the curing accelerator is 0.03 to 2% in the composition of the present invention.
(% By weight, hereinafter the same), more preferably 0.05 to 1%. If the addition amount exceeds 2%, the gelation tends to be too fast and molding tends to be difficult, and if it is less than 0.03%, the curing is slow and the mechanical strength of the cured product tends to be insufficient.

The filler used in the present invention is not particularly limited, and specific examples thereof include crushed silica from natural silica and synthetic silica, crushed quartz such as spherical silica, talc, mica, silicon nitride, alumina, and the like. Is raised. These may be used alone or in combination of two or more.

The amount of the inorganic filler to be used is preferably 250 to 2,000 parts, more preferably 400 to 1600 parts, based on 100 parts (parts by weight, hereinafter the same) of the total amount of the epoxy resin used in the composition of the present invention. If the amount is less than 250 parts, the strength, heat resistance and impact resistance of the obtained cured product will be reduced. If it exceeds 2,000 parts, the flowability of the composition will be reduced and molding will be difficult.

The release agent (internal release agent) used in the present invention is not particularly limited, and specific examples thereof include fatty acids and metal salts thereof, natural wax, synthetic wax, and the like. The amount of the release agent used is preferably 0.5 to 3 parts, more preferably 1.5 to 2.2 parts based on 100 parts of the total amount of the epoxy resin.

The colorant used in the present invention is not particularly limited, and specific examples thereof include a pigment such as carbon black. The amount of colorant used is the total amount of epoxy resin
0.3 to 3.0 parts is preferable with respect to 100 parts, and 0.7 to 1.8 parts is more preferable.

The surface treating agent used in the present invention is not particularly limited, and specific examples thereof include, for example, vinyltrimethoxysilane, glycidyltrimethoxysilane and the like. The amount of surface treatment agent used is 100 total epoxy resin
The amount is preferably from 0.5 to 20 parts, more preferably from 1.2 to 16 parts, per part.

Further, a flame retardant such as antimony trioxide and a desired additive such as an antioxidant may be appropriately compounded in the composition of the present invention.

The composition of the present invention is prepared by subjecting the epoxy resin, curing agent, flexible agent, curing accelerator, filler, release agent, coloring agent, surface treatment agent and, if necessary, components to be used in a usual manner (heating). Roll or the like) and can be formed by a usual method. In addition,
The flexible agent may be used after preliminarily reacting with the epoxy resin as the main component.

The epoxy resin composition for semiconductor encapsulation of the present invention has a modified silicone oil having a hydroxyphenyl group and a copolymer of a modified silicone oil having an epoxy group or a modified silicone oil having a hydroxyphenyl group, and has an epoxy group. Modified silicone oil and 2
The dispersibility of the silicone component in the matrix is further improved by using a novel silicone containing a hydroxyphenyl group at the molecular end and / or inside the molecule consisting of a copolymer with a functional epoxy resin as a flexible agent The cured product is tough and has improved heat resistance and moisture resistance.

Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

Example 1 General formula: The average molecular weight is 1080 and the phenolic hydroxyl equivalent is 50.
130 parts of a modified silicone oil (a ¹ ) having a general formula: And a reaction between 150 parts of a modified silicone oil (b ¹ ) having an average molecular weight of 3250 and an epoxy equivalent of 1600 and 0.5 parts of triphenylphosphine at 150 ° C. for 20 hours while wiping nitrogen. A flexing agent A) was obtained (epoxy group reactivity 97%).

Epoxy resin (EOCN10 manufactured by Nippon Kayaku Co., Ltd.)
20, WPE 200), brominated phenol novolak epoxy resin (BREN-S, WPE280 manufactured by Nippon Kayaku Co., Ltd., phenol novolak resin as a curing agent (PS manufactured by Gunei Chemical Co., Ltd.)
F4261, hydroxyl equivalent 106), curing accelerator (triphenylphosphine), flexible agent, inorganic filler (fused silica (RD-8, manufactured by Tatsumori)), antimony trioxide (Mikuni Smelting Co., Ltd.)
Manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM403), an internal release agent (carnauba wax) and a colorant (carbon black) were mixed in the proportions shown in Table 1, and kneaded with a heating roll to obtain an epoxy resin composition for semiconductor encapsulation.

The obtained composition was subjected to transfer molding (175 ° C, 2
Minutes), a cured test piece was prepared.

Using the obtained test piece, the flexural modulus (JIS K 691
1), bending strength (JIS K 6911), thermomechanical analysis (TMA measurement)
The glass transition temperature, coefficient of thermal expansion and package crack characteristics (using 20 test pieces) after 100 heat cycles (−196 ° C. × 30 seconds to 260 ° C. × 30 seconds) were measured. The results are shown in Table 1.

Having a phenolic hydroxyl group at both terminals of the molecular chain in the same structure as in Example 2-5 modified silicone oil (a ^1), a hydroxyl equivalent 2000 modified silicone oil (a ²⁾ 200 parts of an average molecular weight 4050, modified 20 parts of modified silicone oil (b ² ) having the same structure as silicone oil (b ¹ ) and having epoxy groups at both ends of the molecular chain and having an average molecular weight of 1230 and an epoxy equivalent of 600, and 0.5 part of triphenylphosphine, Pre-reacted product (flexifier B) by reacting at 150 ° C for 20 hours while blowing nitrogen
(Epoxy group conversion 95%).

150 parts of the modified silicone oil (a ² ), 50 parts of the modified silicone oil (b ¹ ) and 0.4 part of triphenylphosphine are reacted at 150 ° C. for 20 hours while wiping nitrogen, and the pre-reacted product (flexible Agent C) was obtained (epoxy group reactivity 98%).

60 parts of the modified silicone oil (a ¹ ) and the general formula: And 100 parts of a modified silicone oil (b ³ ) having an average molecular weight of 12,000, an epoxy equivalent of 2,500, and having an epoxy group inside the molecular chain, and 0.4 part of triphenylphosphine at 150 ° C. for 20 minutes while blowing nitrogen. The reaction was carried out for an hour to obtain a pre-reacted product (flexible agent D) (epoxy group conversion 93%).

Preliminary reaction of 50 parts of flexibilizer B, 100 parts of EOCN1020, and 0.5 part of triphenylphosphine at 150 ° C. for 20 hours while blowing in nitrogen to obtain a flexibilizer E that has reacted with a part of the epoxy resin as a main component. (Hydroxyphenyl group conversion 93
%).

As shown in Table 1, an epoxy resin composition for encapsulating a semiconductor was obtained in the same manner as in Example 1 except that the flexibilizers B to E were used and other components were blended.

Then, a cured test piece was prepared in the same manner as in the example, and the characteristics were examined. The results are shown in Table 1.

Comparative Examples 1-2 Araldite GY29 manufactured by Ciba-Geigy as a flexibilizer
Using 8 (Comparative Example 1) or DER736 (Comparative Example 2) manufactured by Dow Chemical Company, an epoxy resin composition having the composition shown in Table 1 was obtained in the same manner as in Example 1.

Then, a test piece was prepared in the same manner as in Example 1, and the characteristics were examined. The results are shown in Table 1.

Comparative Example 3 An epoxy resin composition having the composition shown in Table 1 was obtained in the same manner as in Example 1 without using a flexibilizing agent.

Then, a test piece was prepared in the same manner as in Example 1, and the characteristics were examined. The results are shown in Table 1.

Reference Examples 1 to 5 300 parts of a modified silicone oil (a ¹ ) and a general formula 20 parts of a bifunctional epoxy resin having an average molecular weight of 380 and an epoxy equivalent of 190 (Epicoat 828, manufactured by Yuka Shell Epoxy Co.) (c ¹ ), and 0.5 part of triphenylphosphine were blown in with nitrogen. Reaction at 150 ° C for 20 hours,
A pre-reacted product (flexible agent F) was obtained (epoxy group conversion 95
%).

200 parts of a modified silicone oil (a ² ) and a bifunctional epoxy having the same structure as the bifunctional epoxy resin (c ¹ ) and having epoxy groups at both ends of the molecular chain, having an average molecular weight of 1600 and an epoxy equivalent of 900. 25 parts of resin (Epicoat 1004, manufactured by Yuka Shell Epoxy) (c ² ) and triphenylphosphine 0.1 part
5 parts were reacted at 150 ° C. for 20 hours while wiping nitrogen to obtain a pre-reacted product (flexible agent G) (epoxy group reaction rate 90%).

General formula: Having a phenolic hydroxyl group at both ends of the molecular chain and inside the molecular chain, 400 parts of a modified silicone oil (a ³ ) having an average molecular weight of about 11,000 and a hydroxyl equivalent of 2300;
26 parts of the functional epoxy resin (c ² ) and 0.4 parts of triphenylphosphine were reacted at 150 ° C. for 20 hours while wiping nitrogen to obtain a pre-reacted product (flexifying agent H) (epoxy group reaction). Rate 83%).

200 parts of modified silicone oil (a ¹ ) and the general formula: And 20 parts of a bifunctional epoxy resin (YX-4000, manufactured by Yuka Shell Epoxy Co., Ltd.) having an epoxy equivalent of 197 and having a biphenyl skeleton (c ³ ), and 0.5 part of triphenylphosphine, while blowing nitrogen thereto. Reaction at 150 ° C for 20 hours,
A pre-reacted product (flexifying agent I) was obtained (epoxy group conversion 93
%).

The pre-reacting agent F50 part, EOCN1020 100 parts and triphenylphosphine 0.5 part were pre-reacted at 150 ° C. for 20 hours while blowing nitrogen, and the pre-reacting agent J preliminarily reacted with a part of the epoxy resin as the main agent. (Hydroxyphenyl group conversion 89
%).

As shown in Table 1, an epoxy resin composition for encapsulating a semiconductor was obtained in the same manner as in Example 1, except that the flexibilizers F to J were used and other components were blended.

Then, a cured test piece was prepared in the same manner as in the example, and the characteristics were examined. The results are shown in Table 2.

As is clear from the results shown in Tables 1 and 2, the cured product of the epoxy resin composition for semiconductor encapsulation of the present invention has high heat resistance, a low coefficient of thermal expansion, and is the same as the conventional one. It can be seen that the glass transition temperature of about or higher has been achieved, and it can be suitably used for semiconductor encapsulation.

[Effects of the Invention] As described above, the epoxy resin composition for semiconductor encapsulation of the present invention comprises a modified silicone oil having a hydroxyphenyl group represented by the general formula (I) as a flexibilizer and a modified silicone oil represented by the general formula (II) Or a modified silicone oil having a hydroxyphenyl group represented by the general formula (I) and a modified silicone oil having an epoxy group represented by the general formula (II) And dispersing the silicone component in the matrix by using a novel silicone having a hydroxyphenyl group at the molecular end and / or inside the molecule comprising a copolymer with the bifunctional epoxy resin represented by the general formula (III) The cured product retains heat resistance and moisture resistance, has low thermal expansion and low elastic modulus. Or in more high glass transition temperature, it is possible to provide a high toughness of the cured product.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location H01L 23/31

Claims (1)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, R ^{1 to} R ³ are each a divalent organic group, R ^{4 to} R ¹⁰ are each an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxyalkyl having 1 to 10 carbon atoms. A group, a phenyl group or a fluorine-substituted alkyl group having 1 to 10 carbon atoms, a
Is an integer of 5-300, b is an integer of 0-10, provided that 0 ≦ [b /
(A + b)] ≦ 0.32) a modified silicone oil having a hydroxyphenyl group, and a general formula (II): (Wherein, R ^{11 to} R ¹³ are each a divalent organic group, R ^{14 to} R ²⁰ are each an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydroxyalkyl having 1 to 10 carbon atoms. Group, a phenyl group or a fluorine-substituted alkyl group having 1 to 10 carbon atoms,
c is an integer of 5-300, d is an integer of 0-10, provided that 0 ≦ [d
/(C+d)]≦0.32) or a copolymer with a modified silicone oil having an epoxy group or the general formula (I)
And a modified silicone oil having an epoxy group represented by the general formula (II) and a modified silicone oil having an epoxy group represented by the general formula (II): (Wherein, R ²¹ and R ²² are each a direct bond or a divalent organic group, e is an integer of 0 to 20, and a hydrogen atom of a benzene ring may be substituted). It contains a terminal and / or internal hydroxyphenyl group-containing silicone composed of a copolymer with an epoxy resin having a group as a flexible agent, and includes an epoxy resin, a curing agent, a curing accelerator, a filler, a release agent,
An epoxy resin composition for semiconductor encapsulation comprising a colorant and a surface treatment agent.